Diammine{N-[2-(hy-droxy-imino)-propion-yl]-N'-[2-(oxidoimino)-propion-yl]propane-1,3-diaminido-κ(4) N,N',N'',N'''}iron(III).

In the title compound, [Fe(C9H13N4O4)(NH3)2], the Fe(III) atom, lying on a mirror plane, is coordinated by four N atoms of a triply deprotonated tetra-dentate N-[2-(hy-droxy-imino)-propion-yl]-N'-[2-(oxidoimino)-propion-yl]propane-1,3-diaminide ligand in the equatorial plane and two N atoms of two ammonia mol-ecules at the axial positions in a distorted octa-hedral geometry. A short intra-molecular O-H⋯O hydrogen bond between the cis-disposed oxime O atoms stabilizes the pseudo-macrocyclic configuration of the ligand. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds into a three-dimensional network. The ligand has a mirror-plane symmetry. One of the methyl-ene groups of the propane bridge is disordered over two sets of sites with equal occupancy factors.

Related literature

For oximes as potential bridging ligands, see: Moroz et al. (2008 ▶, 2010 ▶); Skopenko et al. (1990 ▶). For oximes stabilizing high oxidation states of metal ions, see: Fritsky et al. (1998 ▶, 2006 ▶); Kanderal et al. (2005 ▶). For the coordination chemistry of tetradentate open-chain ligands derived from oximes and amides, see: Duda et al. (1997 ▶); Fritsky et al. (2004 ▶); Kufelnicki et al. (2010 ▶). For related structures, see: Dvorkin et al. (1990a ▶,b ▶); Lampeka et al. (1989 ▶); Mokhir et al. (2002 ▶); Onindo et al. (1995 ▶); Sliva et al. (1997a ▶,b ▶).

Experimental

Crystal data

[Fe(C9H13N4O4)(NH3)2]

M = 331.15

Monoclinic,

a = 8.9111 (3) Å

b = 7.2255 (3) Å

c = 10.6194 (4) Å

β = 108.994 (2)°

V = 646.52 (4) Å3

Z = 2

Mo Kα radiation

μ = 1.19 mm−1

T = 100 K

0.20 × 0.09 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.795, T max = 0.954

12359 measured reflections

1599 independent reflections

1361 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.074

S = 1.04

1599 reflections

124 parameters

H-atom parameters constrained

Δρmax = 0.58 e Å−3

Δρmin = −0.46 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681204826X/hy2607sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681204826X/hy2607Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Fe(C9H13N4O4)(NH3)2]	F(000) = 346.0
Mr = 331.15	Dx = 1.701 Mg m−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 2700 reflections
a = 8.9111 (3) Å	θ = 1.0–27.5°
b = 7.2255 (3) Å	µ = 1.19 mm−1
c = 10.6194 (4) Å	T = 100 K
β = 108.994 (2)°	Block, red
V = 646.52 (4) Å3	0.20 × 0.09 × 0.04 mm
Z = 2

Nonius KappaCCD diffractometer	1599 independent reflections
Radiation source: fine-focus sealed tube	1361 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.047
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 2.4°
φ and ω scans with κ offset	h = −11→11
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	k = −9→9
Tmin = 0.795, Tmax = 0.954	l = −13→13
12359 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.028P)2 + 0.7141P] where P = (Fo2 + 2Fc2)/3
1599 reflections	(Δ/σ)max < 0.001
124 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.84000 (4)	0.7500	0.68148 (4)	0.01316 (12)
O1	1.1762 (2)	0.7500	0.72129 (19)	0.0199 (4)
H1O	1.1180	0.7500	0.6258	0.030*
O2	0.9831 (2)	0.7500	1.07989 (18)	0.0220 (4)
O3	0.4412 (2)	0.7500	0.36943 (19)	0.0196 (4)
O4	0.9952 (2)	0.7500	0.48443 (18)	0.0162 (4)
N5	0.85135 (18)	1.0255 (2)	0.67972 (15)	0.0151 (3)
H5D	0.9063	1.0618	0.6252	0.023*
H5E	0.9016	1.0674	0.7637	0.023*
H5F	0.7514	1.0730	0.6494	0.023*
N1	1.0616 (3)	0.7500	0.7808 (2)	0.0148 (4)
N2	0.8273 (3)	0.7500	0.8580 (2)	0.0149 (4)
N3	0.6183 (3)	0.7500	0.5839 (2)	0.0146 (4)
N4	0.8536 (2)	0.7500	0.5050 (2)	0.0135 (4)
C1	1.1043 (3)	0.7500	0.9092 (3)	0.0166 (5)
C2	1.2708 (3)	0.7500	0.9983 (3)	0.0243 (6)
H2A	1.2741	0.7215	1.0894	0.036*	0.50
H2B	1.3177	0.8722	0.9964	0.036*	0.50
H2C	1.3310	0.6563	0.9681	0.036*	0.50
C3	0.9631 (3)	0.7500	0.9576 (3)	0.0162 (5)
C4	0.6775 (3)	0.7500	0.8870 (3)	0.0191 (6)
H4A	0.6940	0.8119	0.9736	0.023*	0.50
H4B	0.6456	0.6205	0.8952	0.023*	0.50
C5	0.5460 (4)	0.8461 (6)	0.7819 (4)	0.0181 (8)	0.50
H5A	0.5811	0.9733	0.7708	0.022*	0.50
H5B	0.4534	0.8564	0.8136	0.022*	0.50
C6	0.4926 (3)	0.7500	0.6449 (3)	0.0187 (6)
H6A	0.4618	0.6207	0.6555	0.022*	0.50
H6B	0.3981	0.8145	0.5852	0.022*	0.50
C7	0.5789 (3)	0.7500	0.4522 (3)	0.0152 (5)
C8	0.7221 (3)	0.7500	0.4066 (3)	0.0152 (5)
C9	0.7113 (3)	0.7500	0.2641 (3)	0.0229 (6)
H9A	0.7349	0.8742	0.2386	0.034*	0.50
H9B	0.6038	0.7142	0.2092	0.034*	0.50
H9C	0.7880	0.6616	0.2505	0.034*	0.50

	U11	U22	U33	U12	U13	U23
Fe1	0.01225 (19)	0.0146 (2)	0.01244 (19)	0.000	0.00372 (14)	0.000
O1	0.0132 (9)	0.0290 (11)	0.0181 (10)	0.000	0.0062 (8)	0.000
O2	0.0250 (10)	0.0279 (11)	0.0107 (9)	0.000	0.0027 (8)	0.000
O3	0.0121 (9)	0.0254 (11)	0.0183 (10)	0.000	0.0006 (7)	0.000
O4	0.0119 (8)	0.0212 (10)	0.0174 (9)	0.000	0.0073 (7)	0.000
N5	0.0155 (7)	0.0153 (8)	0.0139 (7)	0.0005 (6)	0.0041 (6)	0.0013 (6)
N1	0.0135 (10)	0.0150 (11)	0.0162 (11)	0.000	0.0052 (8)	0.000
N2	0.0150 (10)	0.0172 (11)	0.0131 (10)	0.000	0.0052 (8)	0.000
N3	0.0128 (10)	0.0175 (11)	0.0142 (11)	0.000	0.0053 (8)	0.000
N4	0.0120 (10)	0.0139 (11)	0.0153 (11)	0.000	0.0053 (8)	0.000
C1	0.0172 (13)	0.0147 (13)	0.0147 (12)	0.000	0.0007 (10)	0.000
C2	0.0201 (14)	0.0317 (17)	0.0174 (14)	0.000	0.0011 (11)	0.000
C3	0.0201 (13)	0.0128 (12)	0.0134 (12)	0.000	0.0025 (10)	0.000
C4	0.0181 (13)	0.0229 (14)	0.0181 (13)	0.000	0.0086 (11)	0.000
C5	0.0158 (17)	0.020 (2)	0.0206 (19)	0.0000 (15)	0.0091 (15)	0.0001 (15)
C6	0.0135 (12)	0.0250 (15)	0.0187 (13)	0.000	0.0067 (10)	0.000
C7	0.0147 (12)	0.0127 (12)	0.0174 (12)	0.000	0.0042 (10)	0.000
C8	0.0153 (12)	0.0157 (12)	0.0146 (12)	0.000	0.0048 (10)	0.000
C9	0.0190 (14)	0.0350 (17)	0.0124 (13)	0.000	0.0022 (11)	0.000

Fe1—N3	1.909 (2)	N4—O4i	1.349 (3)
Fe1—N1	1.912 (2)	C1—C2	1.478 (4)
Fe1—N2	1.914 (2)	C1—C3	1.506 (4)
Fe1—N4	1.917 (2)	C2—H2A	0.9800
Fe1—N5	1.9932 (16)	C2—H2B	0.9800
O1—N1	1.364 (3)	C2—H2C	0.9800
O1—H1O	0.9769	C4—C5	1.500 (4)
O2—C3	1.252 (3)	C4—H4A	0.9900
O3—C7	1.255 (3)	C4—H4B	0.9900
O4—O4i	0.000 (4)	C5—C6	1.541 (4)
O4—N4	1.349 (3)	C5—H5A	0.9900
N5—H5D	0.9100	C5—H5B	0.9900
N5—H5E	0.9100	C6—H6A	0.9900
N5—H5F	0.9100	C6—H6B	0.9900
N1—C1	1.291 (3)	C7—C8	1.505 (4)
N2—C3	1.323 (3)	C8—C9	1.485 (4)
N2—C4	1.464 (3)	C9—H9A	0.9800
N3—C7	1.327 (3)	C9—H9B	0.9800
N3—C6	1.465 (3)	C9—H9C	0.9800
N4—C8	1.292 (3)
N3—Fe1—N1	179.44 (10)	C1—C2—H2A	109.5
N3—Fe1—N2	98.66 (9)	C1—C2—H2B	109.5
N1—Fe1—N2	80.78 (9)	H2A—C2—H2B	109.5
N3—Fe1—N4	81.55 (9)	C1—C2—H2C	109.5
N1—Fe1—N4	99.01 (9)	H2A—C2—H2C	109.5
N2—Fe1—N4	179.79 (9)	H2B—C2—H2C	109.5
N3—Fe1—N5	92.39 (4)	O2—C3—N2	127.8 (3)
N1—Fe1—N5	87.63 (5)	O2—C3—C1	120.1 (2)
N2—Fe1—N5	91.64 (5)	N2—C3—C1	112.0 (2)
N4—Fe1—N5	88.35 (5)	N2—C4—C5	112.9 (2)
N3—Fe1—N5i	92.39 (5)	N2—C4—H4A	109.0
N1—Fe1—N5i	87.63 (4)	C5—C4—H4A	109.0
N2—Fe1—N5i	91.64 (5)	N2—C4—H4B	109.0
N4—Fe1—N5i	88.35 (5)	C5—C4—H4B	109.0
N5—Fe1—N5i	173.75 (9)	H4A—C4—H4B	107.8
N1—O1—H1O	104.8	C4—C5—C6	114.8 (3)
Fe1—N5—H5D	109.5	C4—C5—H5A	108.6
Fe1—N5—H5E	109.5	C6—C5—H5A	108.6
H5D—N5—H5E	109.5	C4—C5—H5B	108.6
Fe1—N5—H5F	109.5	C6—C5—H5B	108.6
H5D—N5—H5F	109.5	H5A—C5—H5B	107.5
H5E—N5—H5F	109.5	N3—C6—C5	111.8 (2)
C1—N1—O1	118.8 (2)	N3—C6—H6A	109.3
C1—N1—Fe1	118.60 (18)	C5—C6—H6A	109.3
O1—N1—Fe1	122.60 (16)	N3—C6—H6B	109.3
C3—N2—C4	119.4 (2)	C5—C6—H6B	109.3
C3—N2—Fe1	116.91 (18)	H6A—C6—H6B	107.9
C4—N2—Fe1	123.68 (17)	O3—C7—N3	127.0 (2)
C7—N3—C6	119.2 (2)	O3—C7—C8	120.8 (2)
C7—N3—Fe1	116.37 (17)	N3—C7—C8	112.2 (2)
C6—N3—Fe1	124.43 (17)	N4—C8—C9	124.4 (2)
C8—N4—O4i	121.3 (2)	N4—C8—C7	112.4 (2)
C8—N4—O4	121.3 (2)	C9—C8—C7	123.2 (2)
C8—N4—Fe1	117.49 (18)	C8—C9—H9A	109.5
O4i—N4—Fe1	121.24 (16)	C8—C9—H9B	109.5
O4—N4—Fe1	121.24 (16)	H9A—C9—H9B	109.5
N1—C1—C2	124.4 (3)	C8—C9—H9C	109.5
N1—C1—C3	111.7 (2)	H9A—C9—H9C	109.5
C2—C1—C3	123.9 (2)	H9B—C9—H9C	109.5
N5—Fe1—N1—C1	92.04 (4)	N5—Fe1—N4—C8	−92.66 (4)
N5i—Fe1—N1—C1	−92.04 (4)	N5i—Fe1—N4—C8	92.66 (4)
N5—Fe1—N1—O1	−87.96 (4)	N5—Fe1—N4—O4i	87.34 (4)
N5i—Fe1—N1—O1	87.96 (4)	N5i—Fe1—N4—O4i	−87.34 (4)
N5—Fe1—N2—C3	−87.34 (4)	N5—Fe1—N4—O4	87.34 (4)
N5i—Fe1—N2—C3	87.34 (4)	N5i—Fe1—N4—O4	−87.34 (4)
N5—Fe1—N2—C4	92.66 (4)	C3—N2—C4—C5	149.83 (18)
N5i—Fe1—N2—C4	−92.66 (4)	Fe1—N2—C4—C5	−30.17 (18)
N5—Fe1—N3—C7	87.98 (5)	N2—C4—C5—C6	66.1 (3)
N5i—Fe1—N3—C7	−87.98 (5)	C7—N3—C6—C5	−150.96 (17)
N5—Fe1—N3—C6	−92.02 (5)	Fe1—N3—C6—C5	29.04 (17)
N5i—Fe1—N3—C6	92.02 (5)	C4—C5—C6—N3	−65.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O4	0.98	1.54	2.508 (3)	168
N5—H5D···O4ii	0.91	2.15	3.015 (2)	158
N5—H5E···O2iii	0.91	2.11	2.979 (2)	160
N5—H5F···O3iv	0.91	2.10	2.969 (2)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O4	0.98	1.54	2.508 (3)	168
N5—H5D⋯O4i	0.91	2.15	3.015 (2)	158
N5—H5E⋯O2ii	0.91	2.11	2.979 (2)	160
N5—H5F⋯O3iii	0.91	2.10	2.969 (2)	160

Symmetry codes: (i) ; (ii) ; (iii) .